CN102800878B - Integrated direct fuel cell energy storing and supplying system based on liquid hydrogen storage material - Google Patents

Integrated direct fuel cell energy storing and supplying system based on liquid hydrogen storage material Download PDF

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CN102800878B
CN102800878B CN201110139197.3A CN201110139197A CN102800878B CN 102800878 B CN102800878 B CN 102800878B CN 201110139197 A CN201110139197 A CN 201110139197A CN 102800878 B CN102800878 B CN 102800878B
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storage material
hydrogen storage
fuel cell
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hydrogen
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CN102800878A (en
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程寒松
杨明
倪刚
韩超群
韩波
王圣平
吴金平
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Wuhan hydrogen energy Co., Ltd.
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China University of Geosciences
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Priority to CN201110139197.3A priority Critical patent/CN102800878B/en
Priority to PCT/CN2012/075628 priority patent/WO2012163227A1/en
Priority to EP12792765.5A priority patent/EP2717372A4/en
Priority to KR1020137030454A priority patent/KR20140016966A/en
Priority to JP2014511718A priority patent/JP5759620B2/en
Publication of CN102800878A publication Critical patent/CN102800878A/en
Priority to US14/086,242 priority patent/US20140080026A1/en
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Abstract

The invention relates to a direct fuel cell energy storing and supplying system. An integrated direct fuel cell energy storing and supplying system based on a liquid hydrogen storage material is characterized in that an electrochemical hydrogenation device monomer and a fuel cell monomer are integrated, a working medium inlet of the fuel cell monomer is communicated with a first port of a second three-way valve by a first working medium pipe, a second port of the second three-way valve is communicated with the bottom of a hydrogen storage material hydride tank by a second working medium pipe, a third port of the second three-way valve is communicated with the bottom of a hydrogen storage material tank by a sixth working medium pipe, a working medium outlet of the fuel cell monomer is communicated with a first port of a third three-way valve by a fifth working medium pipe, a second port of the third three-way valve is communicated with the hydrogen storage material hydride tank by a fourth working medium pipe, a third port of the third three-way valve is communicated with the hydrogen storage material tank by a third working medium pipe, and the hydrogen storage material tank contains a hydrogen storage material which is multivariate mixed liquid unsaturated heterocyclic aromatic hydrocarbon. According to the integrated direct fuel cell energy storing and supplying system, not only is the device (with a simple structure) simplified, but also the safety is greatly improved.

Description

A kind of integral type direct fuel cell energy storage energy supplying system based on liquid hydrogen storage material
Technical field
The present invention relates to hydrogen utilization technology in clean energy resource and new energy field.Specifically with the optimized utilizing energy technology that the mutual transformation technology of the storage of Hydrogen Energy and Hydrogen Energy and electric energy is core.Namely carry out electrochemical hydrogenation to realize the storage of electric energy to specifically adding the reversible hydrogen storage material of dehydrogenation, and by direct fuel cell, the Hydrogen Energy in hydrogen storage material hydride is converted into electric energy.Be specifically related to a kind of integral type direct fuel cell energy storage energy supplying system based on liquid hydrogen storage material.
Background technology
The energy is the basis that modern society depends on for existence and development, and the supply capacity substantial connection of the energy the sustainable development of national economy, is one of Strategic Foundation of national security guarantee.Because rapid development of economy causes traditional non-renewable fossil fuel equal energy source to be increasingly in an emergency, countries nowadays government all places hope on the emerging energies such as Hydrogen Energy, solar energy, wind energy, but because these novel energies exist very significant time unsteadiness, thus limit the exploitation of these novel energies.In addition, because causing electrical network electric power when peak of power consumption not enough by the imbalance of power mode, and power surplus during low power consumption, also have impact on making full use of of the existing energy.Because the urgent need of effective utilization of new exploitation of energy resources and traditional energy, the exploitation of technology that countries nowadays is all devoted to " peak load shifting "." peak load shifting " technology is mainly according to adopting storage battery, compressed air and being stored by dump energy in methods such as highland retainings and be used at present.But these methods or because of efficiency not high, or because of the limitation of territorial environment condition, cannot to popularize on a large scale.Hydrogen Energy is pollution-free and energy conversion efficiency is high (reaching as high as 80%), also mutually can transform with electric energy and not be subject to region and environmental limit, if a kind of electric energy-Hydrogen Energy conversion and storing technology of convenience and high-efficiency therefore can be developed, the needs of all kinds of electric power system " peak load shifting " can be widely used in.Be necessary to develop a kind of energy storage energy supply integral system based on Hydrogen Energy for this reason.
We think that system can realize electric energy by following electrochemical reaction and Hydrogen Energy transforms mutually and the storage of energy and supply,
Electrolytic hydrogenation reacts: aromatic ring molecular+H 2o → aromatic ring hydrogenation molecule+O 2(1)
Dehydrogenation exoelectrical reaction: aromatic rings hydrogenation molecule+O 2→ aromatic ring molecular+H 2o (2)
Wherein electrolytic hydrogenation reaction (1) is directly to containing unsaturated bond organic molecule hydrogenation by brine electrolysis, its principle can be illustrated by Fig. 1, anode and the negative electrode that therefrom can find out electrolytic cell are water and aromatic ring molecular respectively, when water is electrolyzed, anode water is decomposed into oxygen and proton, proton by electrolyte diffusion to negative electrode, the hydrogen atom forming ADSORPTION STATE directly and aromatic ring molecular react, make aromatic ring molecular hydrogenation.Be that Hydrogen Energy is stored in hydrogenated aromatic toroidal molecule thus by electric energy conversion.
The principle of above-mentioned electric discharge dehydrogenation reaction (2) as shown in Figure 2, aromatic rings hydrogenation molecule directly generates aromatic ring molecular and proton in the anode generation incomplete oxidation dehydrogenation electric discharge of battery, wherein by electrolyte diffusion to negative electrode, negative electrode reacts with oxygen generation water.Thus the Hydrogen Energy be stored in hydrogenated aromatic toroidal molecule is changed into electric energy.Be not difficult to find out that the product aromatic ring molecular of this process can via reaction (1) hydrogenation and being recycled again.Aromatic ring molecular and hydrogenation molecule thereof serve hydrogen storage material respectively and directly provide the effect of hydrogen source.It can thus be appreciated that the battery that reaction (2) is formed is hydrogenation hydrogen storage material direct fuel cell capable of circulation.Be called R-direct fuel cell (Reversible-direct fuel cell) for simplicity's sake, to be different from the direct fuel cell that existing organic substance is fully oxidized.
Direct fuel cell is fully oxidized, at present mainly alcohol micromolecular direct fuel cell about fuel.The product of its battery is the complete oxidation product C O of alcohol 2and H 2o water, is difficult to its electrolysis is reversed into alcohol and is stored with chemical energy by electric energy.Thus can not be used for " peak load shifting " of above-mentioned electric energy.And have not been reported about the R-direct fuel cell of the above-mentioned cell reaction (2) in the present invention.
Electrochemical catalysis hydrogenation about the unsaturated organic molecule of above-mentioned cell reaction (1) has research from the eighties in 20th century, as Karivmiller equals within 1986,1988, to have studied the electrochemical cathode reduction hydrogenation (Karivmiller in aqueous such as phenanthrene, anthracene, E.and R.I.Pacut (1986) .Tetrahedron 42 (8): 2185-2192./Karivmiller, E., R.I.Pacut, et al. (1988) .Topics in Current Chemistry 148:97-130.); Pintauro equals to have carried out verifying (Pintauro, P.N. & J.R.Bontha (1991) .Journal of Applied Electrochemistry 21 (9): 799-804.) in the electrochemical hydrogenation effect of Raney's nickel electrode to aromatic compounds such as benzene for 1991; Jiang, the people such as J.H utilized in 2006 AB5 type alloy to carry hydrogen material and do electrode catalytic materials, also the electrochemical hydrogenation behavior of p-nitrophenyl is studied (Jiang, J.H.and B.L.Wu (2006) .Journal of Applied Electrochemistry36 (7): 733-738.).These researchs are mainly for the basic research of the electrochemical hydrogenation of unsaturated molecule, not with electric energy to Hydrogen Energy change and storage conveniently carrying out dehydrogenation of discharging is target, the temperature conditions of the kind of therefore selected in the present invention aromatic molecules and physical state thereof, certain embodiments and energy loss etc. thereof all have obvious difference with the above-mentioned research molecule reported, do to make a concrete analysis of discussion below to this.
1) molecule must be not volatile liquid under working temperature (< 150 DEG C), instead of solid.Although for some solid dissolvable in certain solvent, solvent can to reduce its concentration at electrode surface, as the volatile liquid such as solid and benzene such as phenanthrene, anthracene just can not as its working media;
2) desorption temperature of hydrogenation molecule should not be too high, and the hydrogenation Molecular Ring hexane desorption temperature as benzene is greater than 300 DEG C, and this, far beyond the working temperature of battery, should not make working media; Meanwhile, if dehydrogenation hydrogenation temperature is high, the serious polarization of galvanic anode thus the energy loss increased in dehydrogenation electric discharge.As desorption temperature is high, the aromatic ring Small molecular such as the benzene that institute's calorific requirement is large just should not make working media.Unstable molecule in addition as vinyl alcohol can not as working media.
Based on above factor, be necessary that researching and developing novel is liquid at least at the working temperature, the organic liquid hydrogen storage material that its hydride desorption temperature is also enough low, the direct fuel cell energy storage energy supplying system providing a kind of structure simple, novel.
Summary of the invention
The object of the present invention is to provide a kind of integral type direct fuel cell energy storage energy supplying system based on liquid hydrogen storage material, this system has the simple feature of structure.
For achieving the above object, the technical solution used in the present invention is: a kind of integral type direct fuel cell energy storage energy supplying system based on liquid hydrogen storage material, it comprises fuel cell and electrochemical hydrogen gasifying device monomer, and fuel cell is connected with generator, load respectively by AC/DC change-over circuit; It is characterized in that: the structure of electrochemical hydrogen gasifying device monomer is identical with the structure of fuel cell, electrochemical hydrogen gasifying device monomer and fuel cell are integrated, the negative electrode of fuel cell and the anode of electrochemical hydrogen gasifying device monomer share, and the anode of fuel cell and the negative electrode of electrochemical hydrogen gasifying device monomer share; The gentle outlet 17 of water of fuel cell 16 is connected with water pot 20 by outlet pipe 18, and water pot 20 is provided with steam vent (exhaust outlet) 19; One end of first water inlet pipe 21 is connected with the bottom of water pot 20, and the other end of the first water inlet pipe 21 is connected with the first port of the first triple valve 23, and the first water inlet pipe 21 is provided with water pump 22; Second port of the first triple valve 23 is connected by the gentle entrance 26 of the second water inlet pipe 25 and the water of fuel cell 16, and the 3rd port of the first triple valve 23 connects oxygen hose 24; The working medium inlet 13 of fuel cell 16 is connected by first port of the first working media pipe 27 with the second triple valve 30, first working media pipe 27 is provided with working media pump 29, second port of the second triple valve 30 is connected with the bottom of hydrogen storage material hydride tank 32 by the second working media pipe 28, and the 3rd port of the second triple valve 30 is connected with the bottom of hydrogen storage material tank 31 by the 6th working media pipe 37; The working medium exit port 14 of fuel cell 16 is connected by first port of the 5th working media pipe 36 with the 3rd triple valve 35, second port of the 3rd triple valve 35 is connected with hydrogen storage material hydride tank 32 by the 4th working media pipe 34, and the 3rd port of the 3rd triple valve 35 is connected with hydrogen storage material tank 31 by the 3rd working media pipe 33; Described hydrogen storage material tank 31 fills hydrogen storage material, and described hydrogen storage material is the liquid unsaturated heterocycle aromatic hydrocarbons of Diversity.
The liquid unsaturated heterocycle aromatic hydrocarbons of described Diversity is specially the mixing of any one or any two or more in multiple liquid unsaturated heterocycle aromatic hydrocarbon molecule (as: carbazole, N-methyl carbazole, N-ethyl carbazole, indoles, quinoline etc.), is any proportioning during any two above mixing.
Heterocycle in described liquid unsaturated heterocycle aromatic hydrocarbon molecule can be that all rings are heterocycle, may also be part heterocycle, and hetero-atom total quantity scope is 1 to 20; Heterocycle and aromatic ring total quantity are 1 to 20; In single ring in liquid unsaturated heterocycle aromatic hydrocarbon molecule, carbon atom number is 4 to 10.
Hetero-atom in described heterocycle is any one or any two or more in nitrogen, oxygen, sulphur etc.
Described liquid unsaturated heterocycle aromatic hydrocarbon molecule is carbazole, N-methyl carbazole, N-ethyl carbazole, indoles or quinoline etc.
Working media: hydrogen storage material of the present invention (i.e. working media) is nitrogenous in ring, liquid unsaturated heterocycle aromatic hydrocarbons (number of rings is 1 to 20) of the heteroatomic Diversity such as oxygen, sulphur.On aromatic ring containing not homonymy base formed series thick assorted/the mixture liquid hydrogen storage material of aromatic ring aromatic hydrocarbons.Wherein thick assorted/aromatic ring aromatic hydrocarbons number of rings is when being less than 8, its existence form is single organic molecule; When number of rings is 8 ~ 15, its form is oligomer; When number of rings is more than 15, its form is conjugated polymer.Research shows that condensed-nuclei aromatics number of rings is more, and its hydrogenation molecule desorption temperature is lower, and corresponding dehydrogenation is consumed energy also fewer, but its fusing point is higher.In addition, if also containing hetero-atom in ring, then the desorption temperature of condensed-nuclei aromatics hydride also can reduce further, but its fusing point also can raise further.If using the liquid unsaturated heterocycle aromatic hydrocarbons of Diversity as hydrogen storage material, the R-direct fuel coupling of the electrolytic cell of above-mentioned Direct Electrolysis hydrogenation reaction (1) and dehydrogenation exoelectrical reaction (2) can be formed a kind of energy storage energy supply integral system based on Hydrogen Energy.This system works medium (the liquid unsaturated heterocycle aromatic hydrocarbons of Diversity) reusable edible, zero discharge, environmental friendliness, can not be subject to region and environmental limit, thus can meet the urgent need of " peak load shifting " of all kinds of electric power system.The liquid unsaturated heterocycle aromatic hydrocarbons of Diversity in the present invention is in the temperature range of 50 to 280 DEG C, and can realize reversiblely storing hydrogen, hydrogen storage capability can reach 8.0wt%.
Principle of the present invention:
(1) Direct Electrochemistry hydrogenation electrolytic cell
As shown in Figure 1, electrolytic cell reaction is the electrolytic cell principle of Direct Electrochemistry hydrogenation hydrogen storage material: hydrogen storage material molecule+H 2o → hydrogen storage material hydride molecule+O 2electrolytic cell device structure as shown in Figure 3, when cell operation, hydrogen storage material in hydrogen storage material tank (storage tank is separated into hydrogen storage material tank and hydrogen storage material hydride tank by active clapboard) is pumped to cell cathode, during brine electrolysis, be decomposed into oxygen and proton in anode water, proton is reduced to negative electrode by electrolyte diffusion, the hydrogen atom forming ADSORPTION STATE directly with the molecular reaction of organic liquid hydrogen storage material, to make containing unsaturatedly mixing/aromatic ring organic liquid hydrogen storage material obtains hydrogenation.Molecule after hydrogenation enters hydrogen storage material hydride tank.This system can adopt membrane electrode mode to form pile.Each monomer in pile comprises flow-field plate, seal, membrane electrode (as shown in Figure 6, Figure 7).
(2) R-direct fuel cell
R-direct fuel cell is a novel direct fuel cell, and as shown in Figure 2, cell reaction is its principle: hydrogen storage material hydride molecule+O 2→ hydrogen storage material molecule+H 2o.Cell apparatus construction as shown in Figure 4, when the fuel cell is operating, hydrogen storage material hydride in hydrogen storage material hydride tank (storage tank is separated into hydrogen storage material tank and hydrogen storage material hydride tank by active clapboard) is pumped to galvanic anode and directly anode generation dehydrogenation exoelectrical reaction, generate hydrogen storage material molecule and proton, hydrogen storage material molecule flows out electrode and enters hydrogen storage material tank, and proton by electrolyte diffusion to negative electrode, negative electrode reacts with oxygen generation water.This system can adopt membrane electrode mode to form pile.Each monomer in pile comprises flow-field plate, seal, membrane electrode (as shown in Figure 6, Figure 7).
The process inverse process each other of above-mentioned direct fuel cell reaction and Direct Electrochemistry hydrogenation, that is: when there is fuel cell process, system is outwards discharged, and Hydrogen Energy is converted into electric energy; In energising situation, Electrochemical hydriding process occurring, is hydrogen energy storage by electric energy conversion.Energy storage energy supply integral system that is one pollution-free, zero discharge can be formed thus.
The invention has the beneficial effects as follows: above also can as the system with standalone feature based on the electrolytic hydrogenation pond in the direct fuel cell energy storage energy supplying system of liquid hydrogen storage material and R-direct fuel cell, particularly wherein R-direct fuel cell cocoa directly applies to mobile traffic field, as onboard power, compared to existing vehicle-mounted fuel cell system, device greatly simplifies, and this system has the simple feature of structure.Owing to not needing first release hydrogen, not only simplify device, also significantly improve fail safe.Meanwhile, because R-direct fuel dehydrogenation can not cause waste automatically when external circuit is in open circuit, in the convenient battery pile of adjustment at any time, monocell uses number, changes the power output of battery, to adapt to the needs of the random speed change of electric automobile.
Accompanying drawing explanation
Fig. 1 is Electrochemical hydriding schematic diagram.
Fig. 2 is direct fuel cell schematic diagram.
Fig. 3 is Electrochemical hydriding electrolyser construction figure.
Fig. 4 is R-direct fuel cell structure chart.
Fig. 5 is structural representation of the present invention.
Fig. 6 is electric pile structure schematic diagram.
Fig. 7 is liquid stream field plate left view.
Reference numeral: Reference numeral: 1 is gas flow field plate, 2 is seal, 3 is membrane electrode, 9 is liquid stream field plate, and 10 is air flow channel, and 11 is air and water flow passage, 12 is flow channel for liquids, 13 is working media (hydrogen storage material) entrance, and 14 is working medium exit port, and 15 is air cooling unit; 16-fuel cell, the gentle outlet of 17-water, 18-outlet pipe, 19-steam vent, 20-water pot, 21-first water inlet pipe, 22-water pump, 23-first triple valve, 24-oxygen hose, 25-second water inlet pipe, the gentle entrance of 26-water, 27-first working media pipe, 28-second working media pipe, 29-working media pump, 30-second triple valve, 31-hydrogen storage material tank, 32-hydrogen storage material hydride tank, 33-the 3rd working media pipe, 34-the 4th working media pipe, 35-the 3rd triple valve, 36-the 5th working media pipe, 37-the 6th working media pipe.
Embodiment
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
Embodiment 1:
Based on an integral type direct fuel cell energy storage energy supplying system for liquid hydrogen storage material, it comprises fuel cell and electrochemical hydrogen gasifying device monomer; The structure of electrochemical hydrogen gasifying device monomer is identical with the structure of fuel cell, electrochemical hydrogen gasifying device monomer and fuel cell are integrated, fuel cell (being also electrochemical hydrogen gasifying device monomer) is connected with generator, load respectively by AC/DC change-over circuit, the negative electrode of fuel cell and the anode of electrochemical hydrogen gasifying device monomer share, and the anode of fuel cell and the negative electrode of electrochemical hydrogen gasifying device monomer share; The gentle outlet 17 of water of fuel cell 16 is connected with water pot 20 by outlet pipe 18, and water pot 20 is provided with steam vent (exhaust outlet) 19; One end of first water inlet pipe 21 is connected with the bottom of water pot 20, and the other end of the first water inlet pipe 21 is connected with the first port of the first triple valve 23, and the first water inlet pipe 21 is provided with water pump 22; Second port of the first triple valve 23 is connected by the gentle entrance 26 of the second water inlet pipe 25 and the water of fuel cell 16, and the 3rd port of the first triple valve 23 connects oxygen hose 24; The working medium inlet 13 of fuel cell 16 is connected by first port of the first working media pipe 27 with the second triple valve 30, first working media pipe 27 is provided with working media pump 29, second port of the second triple valve 30 is connected with the bottom of hydrogen storage material hydride tank 32 by the second working media pipe 28, and the 3rd port of the second triple valve 30 is connected with the bottom of hydrogen storage material tank 31 by the 6th working media pipe 37; The working medium exit port 14 of fuel cell 16 is connected by first port of the 5th working media pipe 36 with the 3rd triple valve 35, second port of the 3rd triple valve 35 is connected with hydrogen storage material hydride tank 32 by the 4th working media pipe 34, and the 3rd port of the 3rd triple valve 35 is connected with hydrogen storage material tank 31 by the 3rd working media pipe 33; Described hydrogen storage material tank 31 fills hydrogen storage material, and described hydrogen storage material is the liquid unsaturated heterocycle aromatic hydrocarbons of Diversity, and the liquid unsaturated heterocycle aromatic hydrocarbons of Diversity is specially indoles hydrogen storage material, and its hydrogen storage capability is 6.4wt%.
Based on liquid hydrogen storage material integral type direct fuel cell energy storage energy supplying system (two electrode systems) i.e. fuel cell and electrochemical hydrogen gasifying device selected by electrode identical, fuel battery negative pole and electrochemical hydrogen gasifying device anode share, and anode of fuel cell and electrochemical hydrogen gasifying device negative electrode share.System only needs two kinds of electrodes, and be called for short AB type structure, its theory structure as shown in Figure 5.This system can adopt membrane electrode mode to form pile.Each monomer in pile comprises flow-field plate, seal, membrane electrode (as shown in Figure 7).AB type system simple and compact for structure, small volume.
As shown in Figure 5, whole fuel cell is superposed by identical monomer and forms, and each monomer comprises fuel cell gas flow-field plate 1, seal 2, membrane electrode 3, liquid stream field plate 9; One, interval air-cooling apparatus 15 between every two fuel cells.Due to fuel cell process and Electrochemical hydriding process completely reversibility, so each fuel cell is also electrochemical hydrogen gasifying device monomer, in Electrochemical hydriding process, fuel battery negative pole is exactly electrochemical hydrogen gasifying device anode, and anode of fuel cell is also electrochemical hydrogen gasifying device negative electrode.Each parts all there are working media (hydrogen storage material) entrance 13 and working media (hydrogen storage material) export 14, gas flow field plate 1 have air and water flow passage 11, liquid stream field plate 9 has flow channel for liquids 12 (as Fig. 7).
When power surges, to system power supply (charging), there is Electrochemical hydriding process, hydrogen storage material pumps and arrives cathode surface generation hydrogenation through working medium inlet 13 and flow channel for liquids 12 (the second working media pipe 28, the 3rd working media pipe 33 are obstructed from hydrogen storage material tank 31, oxygen hose does not work), hydrogen storage material after hydrogenation flows out from working medium exit port 14, arrives hydrogen storage material hydride tank 32 through pipeline; Water arrives anode surface generation oxygen evolution reaction through air and water flow passage 11.When electric power low ebb, from generation fuel cell process, system is outwards powered (electric discharge), the hydrogen storage material (hydrogen storage material hydride) of hydrogenation arrives anode surface through working medium inlet 13 and flow channel for liquids 12 and dehydrogenation reaction occurs (the 6th working media pipe 37, the 4th working media pipe 34, first water inlet pipe 21 are obstructed, water air pump inoperative), product arrives hydrogen storage material tank 31 through working medium exit port 14; Air arrives cathode surface by air and water flow passage 11 and reacts, and the water of generation enters water pot 20 by pipeline.
Embodiment 2:
Substantially the same manner as Example 1, difference is: the liquid unsaturated heterocycle aromatic hydrocarbons of described Diversity is specially the two end number mixing hydrogen storage material of quinoline, N-ethyl carbazole, the mass ratio of two kinds of components is quinoline: N-ethyl carbazole=2: 3, and its hydrogen storage capability is 5.3wt%.
Embodiment 3:
Substantially the same manner as Example 1, difference is: the liquid unsaturated heterocycle aromatic hydrocarbons of described Diversity is specially the ternary mixed hydrogen storage materials of N-methyl carbazole, quinoline and N-ethyl carbazole, the mass ratio of three kinds of components is N-methyl carbazole: quinoline: N-ethyl carbazole=5: 3: 3, and its hydrogen storage capability is 5.0wt%.
Embodiment 4:
Substantially the same manner as Example 1, difference is: the liquid unsaturated heterocycle aromatic hydrocarbons of described Diversity is specially the quaternary mixed hydrogen storage materials of carbazole, N-methyl carbazole, N-ethyl carbazole and quinoline, the mass ratio of four kinds of components is carbazole: N-methyl carbazole: N-ethyl carbazole: quinoline=4: 3: 5: 1, and its hydrogen storage capability is 6.3wt%.
Embodiment 5:
Substantially the same manner as Example 1, difference is: the liquid unsaturated heterocycle aromatic hydrocarbons of described Diversity is specially the quaternary mixed hydrogen storage materials of carbazole, N-methyl carbazole, N-ethyl carbazole and indoles, the mass ratio of four kinds of components is carbazole: N-methyl carbazole: N-ethyl carbazole: indoles=2: 7: 3: 5, and its hydrogen storage capability is 5.9wt%.
Each raw material of the liquid unsaturated heterocycle aromatic hydrocarbons of the Diversity cited by the present invention can realize the present invention, does not enumerate embodiment at this.

Claims (1)

1. based on an integral type direct fuel cell energy storage energy supplying system for liquid hydrogen storage material, it comprises fuel cell and electrochemical hydrogen gasifying device monomer, and fuel cell is connected with generator, load respectively by AC/DC change-over circuit; It is characterized in that: the structure of electrochemical hydrogen gasifying device monomer is identical with the structure of fuel cell, electrochemical hydrogen gasifying device monomer and fuel cell are integrated, the negative electrode of fuel cell and the anode of electrochemical hydrogen gasifying device monomer share, and the anode of fuel cell and the negative electrode of electrochemical hydrogen gasifying device monomer share; The gentle outlet of water (17) of fuel cell (16) is connected with water pot (20) by outlet pipe (18), and water pot (20) is provided with steam vent (19); One end of first water inlet pipe (21) is connected with the bottom of water pot (20), and the other end of the first water inlet pipe (21) is connected with the first port of the first triple valve (23), and the first water inlet pipe (21) is provided with water pump (22); Second port of the first triple valve (23) is connected with the gentle entrance of water (26) of fuel cell (16) by the second water inlet pipe (25), and the 3rd port of the first triple valve (23) connects oxygen hose (24); The working medium inlet (13) of fuel cell (16) is connected with the first port of the second triple valve (30) by the first working media pipe (27), first working media pipe (27) is provided with working media pump (29), second port of the second triple valve (30) is connected with the bottom of hydrogen storage material hydride tank (32) by the second working media pipe (28), and the 3rd port of the second triple valve (30) is connected with the bottom of hydrogen storage material tank (31) by the 6th working media pipe (37); The working medium exit port (14) of fuel cell (16) is connected by first port of the 5th working media pipe (36) with the 3rd triple valve (35), second port of the 3rd triple valve (35) is connected with hydrogen storage material hydride tank (32) by the 4th working media pipe (34), and the 3rd port of the 3rd triple valve (35) is connected with hydrogen storage material tank (31) by the 3rd working media pipe (33); Described hydrogen storage material tank (31) fills hydrogen storage material, and described hydrogen storage material is the liquid unsaturated heterocycle aromatic hydrocarbons of Diversity;
When cell operation, hydrogen storage material in hydrogen storage material tank is pumped to cell cathode, during brine electrolysis, oxygen and proton is decomposed in anode water, proton is reduced to negative electrode by electrolyte diffusion, directly and the molecular reaction of organic liquid hydrogen storage material, make hydrogen storage material obtain hydrogenation, the molecule after hydrogenation enters hydrogen storage material hydride tank to the hydrogen atom forming ADSORPTION STATE; When the fuel cell is operating, hydrogen storage material hydride in hydrogen storage material hydride tank is pumped to galvanic anode and directly anode generation dehydrogenation exoelectrical reaction, generate hydrogen storage material molecule and proton, hydrogen storage material molecule flows out electrode and enters hydrogen storage material tank, and proton by electrolyte diffusion to negative electrode, negative electrode reacts with oxygen generation water; The liquid unsaturated heterocycle aromatic hydrocarbons of described Diversity is specially any two the above mixing in multiple liquid unsaturated heterocycle aromatic hydrocarbon molecule, is any proportioning during any two above mixing; In described liquid unsaturated heterocycle aromatic hydrocarbon molecule, all rings are heterocycle, and hetero-atom total quantity scope is 1 to 20; Heterocycle total quantity is 1 to 20; In single ring in liquid unsaturated heterocycle aromatic hydrocarbon molecule, carbon atom number is 4 to 10; Hetero-atom in heterocycle is sulphur.
CN201110139197.3A 2011-05-27 2011-05-27 Integrated direct fuel cell energy storing and supplying system based on liquid hydrogen storage material Active CN102800878B (en)

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Application Number Priority Date Filing Date Title
CN201110139197.3A CN102800878B (en) 2011-05-27 2011-05-27 Integrated direct fuel cell energy storing and supplying system based on liquid hydrogen storage material
PCT/CN2012/075628 WO2012163227A1 (en) 2011-05-27 2012-05-17 Hydrogen storage liquid organic material-based direct fuel cell and system for energy storage and energy supply
EP12792765.5A EP2717372A4 (en) 2011-05-27 2012-05-17 Hydrogen storage liquid organic material-based direct fuel cell and system for energy storage and energy supply
KR1020137030454A KR20140016966A (en) 2011-05-27 2012-05-17 Hydrogen storage liquid organic material-based direct fuel cell and system for energy storage and energy supply
JP2014511718A JP5759620B2 (en) 2011-05-27 2012-05-17 Direct fuel cell and energy storage and supply system using organic liquid phase hydrogen storage material
US14/086,242 US20140080026A1 (en) 2011-05-27 2013-11-21 Energy storage and supply system and direct fuel cell based on organic liquid hydrogen storage materials

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CN110820008A (en) * 2019-11-27 2020-02-21 云南电网有限责任公司电力科学研究院 Water electrolytic cell for absorbing hydrogen by organic liquid
CN113745547B (en) * 2021-09-07 2023-08-15 苏州清德氢能源科技有限公司 Direct liquid organic hydrogen carrier fuel cell based on hydrogen storage alloy electrode
CN117936839A (en) * 2024-03-22 2024-04-26 武汉海亿新能源科技有限公司 Multi-path circulating cooling device for fuel cell and control method thereof

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